Process or producing keto compounds from ketones and alkylaminomethanes.



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oesicn E OT'IG CHEMIESOINSEQL G3? ELBERFELD, AND HUGO K ClHLE'R, OF K1?CQ'X'AHfl'IE, GEHdf/IANY,

8:; G0,, 01? ELBEEFELD, G-EREEEANY, A CORPORATION OF ASSIGNOES LEG'FARBENE'ABRIKEN PRDIDUGEK'G E3330 CGZE-HPU'U D5 FROM KETUNES. ANDALKYLAMINO- Ml. lH BlWES.

Mo ilrewingl specification 03! Letters Patent.

Patented Ann. 21, 1914.,

1 0N522 August 19, 1913 concerns the procluction of etc compoundscontaining sz'or inscanc'e the radical:

ce5.co-c -oH1.u g cs, 7 "which have proved to be valuable intermediateproducts for the manuiecsure of erylilu'ene encl its honlologues. It hasnow been found that the homologues of the climethylamiuooxymctlmne andof the tetromethjl diaminoinethnue can also be used for this process.'lhe process for their production.

"proceeds in she some manner as described in U. l. mimosa, of August 19,1913, namely, by treating acct-one and its lioinolog'ues with sdimetliyleminometlione coi'ooouncl, and more particularly with (11-elkyl:iniiuooxymethene or tetraalkyldiem-' inoiuethane, either with orWithout condensing agents, etc. These reactions proceed e. 1 accordingto the following equatlonsz 1 auro a-case sna es-MR):

(R==7sydrogen or ollzyl, B/ ulkyl).

1? sides these products ketocliamins of the formula:

CH9-N(R'): om'-oo-ce GET-ERR): (R=hydmgen or elkyl, R='\1kyl).

These ketocli- I .llgiplicecion fileil May 16, 1913. Serial No. 763,071,

fully the following examples al o given, the parts being by Weight:

' Example l-Procluction of beta -acetylethyldielhylomin osz-co-oehcm-m(Gullah and betaacetyltrimethylenetctraethyldiemin 0B3 00 oH1-N(cnm fromdiebhylal'ninooxymetlione and acetone: 146 part-s ofan aqueousdiethylemin solution per cent.) are gradually dropped into '{5 ports ofaqueous ,iormuldehyde (0 per cent.) which has to be Well stirred andcooled and the soluciou of cliethylaminoo'xy methane thus obtained ismixed with 200 parts of acetone, {l0 parts of bs-ryta water (saturatedat ordinal-y temperature) and 50 parts of Water. This solution is heatedfor several Weeks in an autoclave at 20-30" C until(lietliyleminookymethene can no longer be perceived. The beryta. is thenremoved from the brown solution by satura: tion with carbonic acid or byaddition of bicarbonate and the oil is separated from the aqueoussolution by potash and dried over potash. The excess of acetone isremoved] by distillation in cacao and the re-' meining mistme of basesis decomposed. by a fractional distillation in "vac'lao l;o betaecetylethyldiethylamiu and l Jeta-acetylfirimethylenetet-methyldiamin.he foimer base is e colorless oil having an intense emmoniacel smell,clifllcultly soluble in Water and boils as 72-76 C. 16 111111.); thelatter one represents e coloi le'ss encl .oclorless oil with a littleyellow coloration boiling at 95100 c. (H; mm.).

Exam ale Jr-Production of beta-acetyletliylcllelihylamin andbets-acetyltrimethylenetetraethyldiamin from tetraethyldiaminometheneand acetone: 750 parts of aqueous formaldehyde (Q0 per cent.) aregradually dropped into 3245 parts of aqueous dietliylamin solution (4-5per cent.) which is being stirred and cooled and 2000 parts of acetone,soc ports of barytwwater (seturetcoi at ordinary" temperature) and 500is added to the brown solution in order to remove the baryta.Bariulncarbonate is removed by filtration. The oil is separated withpotash "from the filtrate, dried and worked up as described in thepreceding example.

Example 3Production of beta-acetylpropyldiethylamin f andbeta-beta-acetyl-methyl-tri1nethylenetetraethyldiamin cEn-oo-o cH fromdiethylaminooxymethane and methylethylketonez 1&6 parts an aqueousdiethylamin solution (50 per cent.) are gradually dropped into 75 partsof aqueous formaldehyde (4:0per cent.) which hastobe well stirred andcooled and this solution is then mixed with 216 parts ofmethylethylketone and 50 parts of sodium lye (0.3 per cent). When themixture is allowed to stand for several days at ordinary temperature thereaction is finislled. The free alkali is removed from the brownsolution by saturation with carbonic 'acidorby addition of bicarbonateand the oil is separated from the aqueous solution by potash and driedover potash. The excess of methylethylketone is now distilled offadvantageously under somewhat reduced pressure in an. apparatus suitablefor fractional distillation and the remaining mixture of bases isdecomposed by a fractional istillation in vacuo tobeta-acetyl-propyldiethylamin and beta-beta-acetyl-methyttrimethylenetetraethyldiamin.

,- represents a colorless oil with a little ammoniacal smell,difiicultly soluble inwater,

" boiling at 7748" C. (16 mm), the latter is a thick, yellowish almostodorless oil which boils at 105110 C. (7 mm.)

The sodium lye can be replaced with the same success by baryta-water. I

Example 1Production of the same bases with the aid oftetraethyldiaminomethane:

' 292 parts of an aqueous diethylai'nin solution per cent.)arelgradually dropped into 75 parts of aqueous: formaldehyde (40 50 percent.) while well st irred and cooled. This mixture forming two layers,is mixed with 210 parts of methylethylketone and boiled on the refluxcondenser for so long a time until a test portion after acidulation withacetic acid is not' any morerendered turbid by a solution of anilinacetate'which requires about some hours. The solution is then dehydratedwith potasln-and worked up in the same manner as described in Ex- 6ample 1, whereby the same result is obtained as described in thisexample.

The methylethylketone can be naturally replaced with the same success byacetone. ilin the same manner the mixed tetraalkyldi- 6 aminomethanes,obtained from two different The former dialkylamins, a molecule offormaldehyde in aqueous solution and acetone or its homologues can beused. A mixture of the known R(.O--KI.(,HQ.\\RI where R is alkyl, 0. 9.,methyl, and Where R represents alkyl. g. ethyl or other alkyl groupshaving more than one carbon atom therein.

In our copending; application Serial No. 768,072 we. have claimedspecifically the use of the higher tetraalkyldiaininomethane for formingthe above described kcto compounds, while the claims of the present application are drawn generically to the use of the higherdialkylaminomethane compounds and specifically to the use of the higherdia1kylaminooxymethanes, such as diethylaminooxymethane, etc.

\Ve claiinz- 1. The process of producing a polyalkylamino-substitutedketo compound which coinprises reacting on a hetone with a.diallrylaminomethane compound in which the alkyl groups contain. morethan one carbon. atom.

2. The process of producing a dialkylamino substituted-ketone whichcomprisesreacting on a ketone with dialkylaminooxymethane in which thealkyl groups contam more than one carbon atom.

3. The process of producing a po lyalkylamino-substituted lreto compoundwhich comprises reacting on a ketone with a dialkylaminooxymethanecompound in which the alkyl groups contain more than one carbonatom withthe addition of a condensing agent.

4. The process of producing a dialkylamino-substituted keto compoundwhich comprises reacting on a ketone with dialkylaminooxymethane inwhich the alkyl groups contain more than one carbon atom with t additionof a condensing agent.

5. The process of producing a polyalkylamino-substituted keto compoundwhich comprises-reacting on a ketonc with a dialkylaminomethane compoundin which the alkyl groups contain more than one carbon atom with theaddition of an inorganic base as a condensing agent.

6. The process of producing a polyalkylamino-substituted ketone whichcomprises pounds containing the group:

ethyl ethyi which comprises treating a methyl ketone with adiethylaminomethane compound.

8. The process of producing ketocom ethyl I cn,-co-d :-oH,-N whichcomprises treatin a methylketone with diethylaminooxyinet ane,

9. The process of producing keto com pounds containing the nucleus whichcomprises treating a methyl-ketone with a diethylaminomethane com ound.

10. The process of producing eto compounds containing the nucleus whichcomprises treating a methyl-ketone with a diethylaminomethane compoundwith the addition of an'inorganic base as a condensing agent.

11.- The process of producing keto compounds containing the radical ornucleus which comprises treating a ketone with diethylaminooxymethane.

' pounds containing-the group:

which comprises treatingl 12. The process of producing keto com-' poundscontaining the radical or nucleus I which comprises treating a 'ketonewith diethylaminooxymethane with the addition of a condensing agent.

13. The process of producing keto cornwhich comprises treating a methylketone with adiet laminomethane compound until the .twoold introductionof the group I I l)I I has been efiectedQ 14. The process of producingketo compounds containing the group:

r cm-mom. CHr-CO- Hg-N(C;H.) I a meth 1 ketone with diethylaminooxymetane unti the twofold introduction of the group:

-CH2 (C2H6)S has Been eflected. .In testimony whereof we have hereunto.set our hands in the presence of two subscribing witnesses. I

GEORG MERLING. 1; 5. or'ro cHRzEscINsKI. {13.8.1 KijHLER. -[L.s.]Witnesses:

IIELEN Norma, Annual: Norm.

